Optical article containing a linear condensation polymer exhibiting a high level of second order polarization susceptibility

Abstract

An optical article is disclosed containing, for the transmission of electromagnetic radiation, a medium exhibiting a second order polarization susceptibility greater than 10 -9 electrostatic units comprised of a linear polymer containing polar aligned noncentrosymmetric molecular dipoles having an electron donor moiety linked through a conjugated π bonding system to an electron acceptor moiety to permit oscillation of the molecular dipole between a ground state exhibiting a first dipole moment and an excited state exhibiting a differing dipole moment. The linear polymer is a condensation polymer including in its backbone a plurality of molecular dipoles including sulfonyl electron acceptor moieties sequentially arranged to reinforce electron displacement along the polymer backbone.

What is claimed is: 
     
       1. An optical article containing, for the transmission of electromagnetic radiation, a medium exhibiting a second order polarization susceptibility greater than 10 -9  electrostatic units comprised of a linear polymer containing polar aligned noncentrosymmetric molecular dipoles each having an amino, oxy or thio electron donor moiety linked through a conjugated π bonding system to a sulfonyl electron acceptor moiety to permit oscillation of the molecular dipole between a ground state exhibiting a first dipole moment and an excited state exhibiting a differing dipole moment, characterized in that the linear polymer is a condensation polymer including in its backbone the electron donor moiety, the conjugated π bonding system, and the electron donor moiety of each of a plurality of the molecular dipoles and the molecular dipoles in the polymer backbone being relatively oriented to reinforce electron displacement along the polymer backbone.   
     
     
       2. An optical article according to claim 1 further characterized in that means are provided for directing electromagnetic radiation to said transmission medium. 
     
     
       3. An optical article according to claim 1 further characterized in that biasing means are provided for directing electromagnetic radiation across said transmission medium. 
     
     
       4. An optical article according to claim 3 further characterized in that said biasing means includes at least one transparent electrode in contact with said transmission medium. 
     
     
       5. An optical article according to claim 1 further characterized in that said transmission medium lies in contact with a linear waveguide for electromagnetic radiation. 
     
     
       6. An optical article according to claim 1 further characterized in that the molecular dipoles in the polymer backbone are oriented so that the sulfonyl electron acceptor and amino, oxy or thio electron donor moieties of each molecular dipole are relatively displaced in the same direction along the polymer backbone. 
     
     
       7. An optical article according to claim 1 further characterized in that the molecular dipoles containing sulfonyl electron acceptor moieties in the polymer backbone are derived from monomers satisfying the formula: ##STR14## where A and B represent a pair of interactive functional groups capable of supporting a condensation polymerization reaction, D is an amino, oxy or thio electron donor moiety,   E is a conjugated π bonding system, and   R is a divalent hydrocarbon moiety.   
     
     
       8. An optical article according to claim 1 further characterized in that the molecular dipoles containing sulfonyl electron acceptor moieties in the polymer backbone are derived from monomers satisfying the formula: ##STR15## where A and B represent a pair of interactive functional groups capable of supporting a condensation polymerization reaction, E is a conjugated π bonding system,   R is a divalent hydrocarbon moiety,   R 1  is hydrogen or a hydrocarbon moiety,   R 2  is a hydrocarbon moiety, or   R 1  and R 2  together complete a cyclic amino moiety, and   m is 0 or 1.   
     
     
       9. An optical article according to claim 1 further characterized in that the molecular dipoles containing sulfonyl electron acceptor moieties in the polymer backbone are derived from monomers satisfying the formula: ##STR16## where A and B represent a pair of interactive functional groups capable of supporting a condensation polymerization reaction, E is a conjugated π bonding system,   R is a divalent hydrocarbon moiety,   R 3  is a hydrocarbon moiety, and   X is oxygen or sulfur.   
     
     
       10. An optical article according to claim 1 further characterized in that the molecular dipoles containing sulfonyl electron acceptor moieties in the polymer backbone are derived from monomers satisfying the formula: ##STR17## where A and B represent a pair of interactive functional groups capable of supporting a condensation polymerization reaction, D is an amino, oxy or thio electron donor moiety,   G is independently in each occurrence methine or aza,   n is 4 to 20, and   R is a divalent hydrocarbon moiety.   
     
     
       11. An optical article according to claim 1 further characterized in that the molecular dipoles containing sulfonyl electron acceptor moieties in the polymer backbone are derived from monomers satisfying the formula: ##STR18## where A and B represent a pair of interactive functional groups capable of supporting a condensation polymerization reaction, D is an amino, oxy or thio electron donor moiety,   G is independently in each occurrence a methine or aza moiety, with the proviso that no more than two aza moieties are next adjacent,   n is an integer of from 1 to 3,   R is a divalent hydrocarbon moiety,   R a  represent hydrogen or substituents no one of which have a Hammett sigma value more positive than the sulfonyl group SO 2  R and which together, without inclusion of the sulfonyl group SO 2  R, provide a positive net Hammett sigma value, and   R d  represent hydrogen or substituents no one of which have a Hammett sigma value more negative than the electron donor D and which together, without inclusion of the electron donor D, provide a negative net Hammett sigma value.   
     
     
       12. An optical article according to claim 1 further characterized in that the molecular dipoles containing sulfonyl electron acceptor moieties in the polymer backbone are derived from monomers satisfying the formula: ##STR19## where A and B represent a pair of interactive functional groups capable of supporting a condensation polymerization reaction, D is an amino, oxy or thio electron donor moiety,   G is independently in each occurrence a methine or aza moiety, with the proviso that no more than two aza moieties are next adjacent,   p is 0 or 1,   R is a divalent hydrocarbon moiety,   R a  represent hydrogen or substituents no one of which have a Hammett sigma value more positive than the sulfonyl group SO 2  R and which together, without inclusion of the sulfonyl group SO 2  R, provide a positive net Hammett sigma value, and   R d  represent hydrogen or substituents no one of which have a Hammett sigma value more negative than the electron donor D and which together, without inclusion of the electron donor D, provide a negative net Hammett sigma value.   
     
     
       13. An optical article according to claim 1 further characterized in that the molecular dipoles containing sulfonyl electron acceptor moieties in the polymer backbone are derived from monomers satisfying the formula: ##STR20## where A and B represent a pair of interactive functional groups capable of supporting a condensation polymerization reaction, G is independently in each occurrence a methine or aza moiety, with the proviso that no more than two aza moieties are next adjacent,   R is a divalent hydrocarbon moiety,   R a  represent hydrogen or substituents no one of which have a Hammett sigma value more positive than the sulfonyl group SO 2  R and which together, without inclusion of the sulfonyl group SO 2  R, provide a positive net Hammett sigma value,   R d  represent hydrogen or substituents no one of which have a Hammett sigma value more negative than the electron donor D and which together, without inclusion of the electron donor D, provide a negative net Hammett sigma value, and   q is an integer of from 0 to 3.   
     
     
       14. An optical article according to claim 1 further characterized in that the molecular dipoles containing sulfonyl electron acceptor moieties in the polymer backbone are derived from monomers satisfying the formula: ##STR21## where A is a halogen substituent, B is an active hydrogen,   E is a conjugated π bonding system,   R is a divalent hydrocarbon moiety, and   R 1  is a hydrocarbon moiety.   
     
     
       15. An optical article according to claim 1 further characterized in that the the linear polymer is a homopolymer. 
     
     
       16. An optical article according to claim 1 further characterized in that the conjugated π bonding system is comprised of a stilbenoid moiety. 
     
     
       17. An optical article according to claim 16 further characterized in that the stilbenoid moiety is a divalent 4,4'-stilbene moiety.